Tuning of electronic properties in thienyl-phosphole pi-conjugated systems through P-functionalization monitored by Raman spectroscopy

Chemistry : a European Journal
Juan CasadoJuan T López Navarrete

Abstract

Herein, a Raman spectroscopic study of a new family of 2,5-di(2-thienyl)phospholes and thienyl-capped 1,1'-diphospholes is presented. The Raman spectra have been carefully assigned with the help of density functional calculations. For di(2-thienyl)phospholes, two well-differentiated groups of Raman bands exist that arise either from the central phosphole ring or from the outer thiophene substituents. These data reveal a segmentation of the electronic structure. This paper reports interesting relationships between geometrical data such as the BLA (bond-length alternation) parameter and Raman band wavenumbers. These correlations are unprecedented in the chemistry of phospholes and have been used to interpret the evolution of the electronic structure (aromaticity=pi-conjugation) upon 1) substitution of the central sulfur atom of terthiophene by phosphorus and 2) P-functionalization. Increasing the coordination number of the phosphole ring results in intramolecular charge transfer. The best scenario for phosphole aromaticity is found for 1,1'-diphospholes.

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Citations

Jul 7, 2007·Chemistry : a European Journal·Tomohiro AgouTakayuki Kawashima
Dec 4, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Jeanne Crassous, Régis Réau
Mar 21, 2009·Organic & Biomolecular Chemistry·Yoshihiro Matano, Hiroshi Imahori
Apr 22, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Alvaro DíezSergio Sánchez
Nov 10, 2006·Chemical Reviews·Thomas Baumgartner, Régis Réau
Dec 5, 2014·The Journal of Physical Chemistry. a·Sergey A KatsyubaOleg G Sinyashin
Nov 16, 2006·Journal of the American Chemical Society·Joseph G CordaroHansjörg Grützmacher

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